Fungicidal, miticidal and ovicidal alkoxycarbonylalkyl-substituted and carbamylalkyl-substituted N-haloalkylthiosulfonamides

ABSTRACT

Fungi, mites and mite eggs are killed by applying thereto sulfonamides of the formula ##STR1## wherein R and R 1  individually are alkyl, cycloalkyl, aryl, carbamylalkyl, or alkoxycarbonylalkyl and R 2  is haloalkyl, with the proviso that one R or R 1  group is carbamylalkyl or alkoxycarbonylalkyl.

This application is a division of Ser. No. 921,385, filed July 3, 1978now U.S. Pat. No. 4,230,875, which in turn is a division of Ser. No.734,858, filed Oct. 22, 1976, now U.S. Pat. No. 4,112,237.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,178,447, issued to G. K. Kohn on Apr. 13, 1965,discloses the fungicidal activity of N-polyhaloethylthio-substitutedaryl- and alkanesulfonamides.

U.S. Pat. No. 2,779,788, issued to H. Gysin et al on Jan. 29, 1957,discloses fungicidal N-trichloromethylthio-substitutedchloromethanesulfonamides.

U.S. Pat. No. 3,925,555, issued to I. Okuda et al on Dec. 9, 1975,discloses the control of mites with chloromethanesulfonamides.

DESCRIPTION OF THE INVENTION

The compounds of the invention are represented by the formula ##STR2##wherein R and R¹ individually are alkyl of 1 to 6 carbon atoms;cycloalkyl of 5 to 8 carbon atoms substituted with up to 2 alkyl of 1 to4 carbon atoms; phenyl substituted with up to 2 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, trifluoromethyl,trichloromethyl, tribromomethyl, or alkyl of 1 to 4 carbon atoms;alkoxycarbonylalkyl of 2 to 6 carbon atoms; carbamylalkyl of 1 to 6carbon atoms; N-alkylcarbamylalkyl of 2 to 6 carbon atoms; orN,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms and R² is haloalkyl of 1to 2 carbon atoms and of 1 to 5 fluoro, chloro, bromo or iodo, with theproviso that one R or R¹ group is alkoxycarbonylalkyl, carbamylalkyl of1 to 6 carbon atoms, N-alkylcarbamylalkyl of 2 to 6 carbon atoms, orN,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms.

Representative alkyl groups which R and R¹ may represent include methyl,ethyl, propyl, isopropyl, butyl, hexyl, etc. Representative cycloalkyland alkylcycloalkyl groups which R and R¹ may represent includecyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2,4-dimethylcyclohexyl,4-ethylcyclohexyl, cycloheptyl, cyclooctyl, 5-methylcyclooctyl, etc.Representative aryl groups which R and R¹ may represent include phenyl;substituted phenyl such as 4-fluorophenyl, 2-chlorophenyl, 4-iodophenyl,2,4-dibromophenyl, 2,4-dimethylphenyl, 2-methyl-4-chlorophenyl,trifluoromethylphenyl, etc.

Representative R² groups are fluoromethyl, chloromethyl, iodomethyl,dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl,1,1,1-trichloroethyl, 1,1,2,2-tetrachloroethyl, 1,2,2,2-tetrachloroethyland pentachloroethyl.

Representative alkoxycarbonylalkyl R and R¹ groups aremethoxycarbonylmethyl, ethoxycarbonylmethyl, n-butoxycarbonylmethyl,1-(methoxycarbonyl)ethyl and 3-(methoxycarbonyl)propyl. Representativecarbamylalkyl R and R¹ groups are carbamylmethyl, carbamylethyl,N-alkylcarbamylalkyl of 2 to 6 carbon atoms, such asN-methylcarbamylmethyl and N-ethylcarbamylmethyl, andN,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms, such asN,N-dimethylcarbamylmethyl and 1-(N,N-diethylcarbamyl)ethyl.

Preferred alkyl R or R¹ groups are alkyl of 1 to 3 carbon atoms.Preferred cycloalkyl R or R¹ groups are cycloalkyl of 5 to 6 carbonatoms substituted with up to 2 alkyl of 1 to 4 carbon atoms. Preferredaryl R or R¹ groups are phenyl and phenyl-substituted with 1 to 2 of thesame or different substituents selected from fluoro, chloro, bromo,trifluoromethyl or alkyl of 1 to 4 carbon atoms.

The preferred alkoxycarbonylalkyl R and R¹ groups arealkoxycarbonylmethyl and 1-(alkoxycarbonyl)ethyl of 2 to 4 carbon atoms.The preferred carbamylalkyl R and R¹ groups are N,N-dialkylcarbamylalkylof 3 to 6 carbon atoms. The preferred R² groups are haloalkyl of 1 to 2carbon atoms and of 1 to 5 chloro or bromo. The most preferred R² groupsare trichloromethyl and tetrachloroethyl.

One class of preferred compounds of formula (I) is that wherein one R orR¹ group is alkoxycarbonylalkyl, carbamylalkyl, N-alkylcarbamylalkyl orN,N-dialkylcarbamylalkyl and the other R or R¹ group is alkyl,cycloalkyl or aryl as defined above.

Another preferred class of compounds is that wherein R isalkoxycarbonylalkyl and R¹ is phenyl substituted with up to 2 of thesame or different substituents selected from fluoro, chloro, bromo,trifluoromethyl or alkyl of 1 to 4 carbon atoms.

Another preferred class of compounds is that wherein R is alkyl of 1 to6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms substituted with up to2 alkyl of 1 to 4 carbon atoms, or phenyl substituted with up to 0.2 ofthe same or different substituents selected from fluoro, chloro, bromo,trifluoromethyl, or alkyl of 1 to 4 carbon atoms and R¹ group isalkoxycarbonylalkyl of 2 to 6 carbon atoms.

Representative compounds of the invention include:

N-methoxycarbonylmethyl-N-(1,1,2,2-tetrafluoroethylthio)methanesulfonamide

N-n-propoxycarbonylmethyl-N-(trichloromethylthio)-4-chlorophenylsulfonamide

N-[1(-methoxycarbonyl)ethyl]-N-(1,1,2,2-tetrabromoethylthio)isopropanesulfonamide

N-ethoxycarbonylmethyl-N-(fluoromethylthio)-2-chloroethanesulfonamide

N-ethyl-N-(1,1,2,2-tetrachloroethylthio)-methoxycarbonylmethanesulfonamide

N-chloromethyl-N-(2,2,2-triiodoethylthio)-(1-methoxycarbonyl)ethanesulfonamide

N-butoxycarbonylmethyl-N-(dichloromethylthio)cyclohexanesulfonamide

N-cyclohexyl-N-(1,1,2,2-tetrachloroethylthio)ethoxycarbonylmethanesulfonamide,

N-methoxycarbonylmethyl-N-(1,1,2,2-tetrachloroethylthio)-4-chlorophenylsulfonamide,

N-2-fluorophenyl-N-(1,1,2,2-tetrachloroethylthio)-methoxycarbonylmethanesulfonamide,

N-2-trifluoromethylphenyl-N-(1,1,2,2-tetrachloroethylthio)carbamylmethanesulfonamide,and

N-methoxycarbonylmethyl-N-(trichloromethylthio)methylcarbamylmethanesulfonamide.

The compounds of the invention are prepared by sulfenylating asulfonamide of the formula R-SO₂ -NHR¹ (II), wherein R and R¹ have thesame significance as previously defined, with a haloalkylsulfenylchloride of the formula R² SCl (III) wherein R² has the samesignificance as previously defined. The sulfenylation reaction isgenerally conducted by reacting substantially equimolar quantities ofthe sulfonamide (II) and the sulfenyl chloride (III) in the liquid phasein the presence of an acid acceptor. Suitable acid acceptors are organicamines such as pyridine compounds, e.g., pyridine or alpha-picoline, andlower trialkylamines, e.g., triethylamine or tributylamine, andinorganic alkali metal hydroxides, e.g., sodium hydroxide or potassiumhydroxide. Generally, at least one mol of acid acceptor is employed foreach mol of sulfenyl chloride (III). The reaction is normally conductedin an inert liquid diluent, e.g., organic solvents such as chlorinatedhydrocarbons.

The sulfenylation reaction may be conducted in the presence of catalyticamounts of a quaternary ammonium salt. Generally, amounts of quaternaryammonium salt per mol of the sulfenyl chloride (III) reactant vary fromabout 0.01 to 0.3, although amounts from 0.05 to 0.2 mol per mol of thesulfenyl chloride (III) are preferred. Suitable quaternary ammonium saltare tetraalkylammonium halides wherein the alkyl has 1 to 6 carbon atomsand the halide is fluoro, chloro, bromo or iodo, e.g.,tetramethylammonium chloride or tetrabutylammonium bromide.

The sulfenylation reaction is conducted at a temperature of 0° C. to theboiling point of the diluent, although temperatures between 0° C. and100° C. are preferred. The reaction is conducted at or above atmosphericpressure. The reaction time will, of course, vary depending on thereaction temperature and the particular reactants employed. Generally,the reaction is completed within one-half to 24 hours. The product (I)is isolated and purified by conventional procedures such as extraction,filtration, crystallization and chromatography.

The sulfenylation reaction may also be conducted with an alkali metalsalt of the sulfonamide (II) and the haloalkyl sulfenyl chloride (III)by conventional procedures.

MITE OVICIDAL ACTIVITY

The compounds of the invention have been found to be useful andeffective for the killing of mite eggs. Some compounds of the inventionare also useful and effective for the killing of mites.

Any conventional techniques or methods can be employed for contactingmites or mite eggs with an effective miticidal or ovicidal amount of thecompounds of the invention. Like most agricultural chemicals, they arenot usually applied full strength, but are generally incorporated withconventional biologically inert extenders or carriers normally employedfor facilitating dispersion of active ingredients for agriculturalchemical applications, recognizing the accepted fact that theformulation and mode of application may affect the activity of amaterial. The toxicants of this invention may be applied as sprays,dusts, or granules to the mites or mite eggs, their environment or hostssusceptible to mite attack. They may be formulated as granules of largeparticle size, as powdery dusts, as wettable powders, as emulsifiableconcentrates, as solutions, or as any of several other known types offormulations, depending on the desired mode of application.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersant. These compositionsnormally contain from 5-80% toxicant and the rest inert material whichincludes dispersing agents, emulsifying agents, and wetting agents. Thepowder may be applied to the soil as a dry dust or preferably as asuspension in water. Typical carriers include fuller's earth, kaolinclays, silicas, and other highly absorbent, readily wet, inorganicdiluents. Typical wetting, dispersing, or emulsifying agents used inagricultural formulations include, for example, the alkyl and alkylarylsulfonates and sulfonates and their sodium salts; alkylamide sulfonates,including fatty methane taurides, alkylaryl polyether alcohols, sulfatedhigher alcohols, and polyvinyl alcohols; polyethylene oxides; sulfonatedanimal and vegetable oils; sulfonated petroleum oils; fatty acid estersof polyhydric alcohols and the ethylene oxide addition products of suchesters; and the addition products of long chain mercaptans and ethyleneoxide. Many other types of useful surface active agents are available incommerce. The surface active agent, when used, normally comprises fromone percent to fifteen percent by weight of the pesticidal composition.

Dusts are freely flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, pyrophyllite,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, and other organic and inorganic solidswhich act as dispersants and carriers for the toxicant. These finelydivided solids have an average particle size of less than about fiftymicrons. A typical dust formulation useful herein contains 75% silicaand 25% of the toxicant.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions which are readily dispersedin water to other dispersant, and may consist entirely of the toxicantwith a liquid or solid emulsifying agent, or may also contain a liquidcarrier, such as xylene, heavy aromatic naphthas, isophorone, and othernon-volatile organic solvents. For application these concentrates aredispersed in water or other liquid carrier, and normally applied as aspray to the area to be treated.

The percentages by weight of the toxicant may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprises 0.5% to 95% of the toxicant byweight of the pesticidal composition.

The compositions may be formulated and applied with other activeingredients, including nematocides, insecticides, fungicides,bactericides, plant growth regulators, fertilizers, etc. In applying thechemical an effective amount and concentration of the toxicants of thisinvention is, of course, employed.

FUNGICIDAL UTILITY

The compounds of the invention are also useful for controlling fungi,particularly plant fungal infections caused by Botrytis cinerea, leafblights caused by organisms such as Pythrium ultimum, Helminthosporumsativum, Fusarium moniliforme, Rhizoctonia solani, Monolinia fructicolaand Uromyces phaseoli typica. However, some fungicidal compounds of theinvention may be more fungicidally active than others against particularfungi.

When used as fungicides, the compounds of the invention are applied infungicidally effective amounts to fungi and/or their habitats, such asvegetative hosts and non-vegetative hosts, e.g., animal products. Theamount used will, of course, depend on several factors such as the host,the type of fungus and the particular compound of the invention. Thefungicides of the invention are generally incorporated with conventionalbiologically inert extenders or carriers normally employed forfacilitating dispersion of active fungicidal compounds. Thus, thefungicides of the invention may be formulated and applied as granules,as powdery dusts, as wettable powders, as emulsifiable concentrates, assolutions, or as any of several other known types of formulations,depending on the desired mode of application.

The percentages by weight of the fungicide may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprise 0.5% to 95% of the toxicant byweight of the fungicidal composition.

The fungicidal compositions may be formulated and applied with otheractive ingredients, including other fungicides, insecticides,nematocides, bactericides, plant growth regulators, fertilizers, etc.

EXAMPLES EXAMPLE 1 Preparation ofN-methoxycarbonylmethyl-N-trichloromethylthiobenzenesulfonamide

A 47.5 g (0.6 mol) sample of pyridine was added dropwise to a stirredand cooled (ice bath) slurry of 53.0 g (0.3 mol) benzenesulfonylchloride and 37.7 g (0.3 mol) glycine methyl ester hydrochloride in 500ml dichloromethane. The reaction mixture was then allowed to warm to 25°C. and was stirred for about 16 hours. The reaction mixture was dilutedwith 250 ml water, the organic layer was separated, washed with water,washed with 10% aqueous hydrochloric acid solution, washed with water,dried over magnesium sulfate and evaporated to give 36.5 gN-(methoxycarbonylmethyl)benzenesulfonamide, which crystallized as acolorless solid melting at 62°-63° C.

A 3.5 g (0.035 mol) sample of triethylamine was added dropwise to asolution of 8 g (0.035 mol) N-methoxycarbonylmethyl)benzenesulfonamideand 6.5 g (0.035 mol) trichloromethylsulfenyl chloride in 150 mldichloromethane. The reaction mixture was then stirred at about 25° C.for about 1 hour, washed with water, dried over magnesium sulfate andevaporated to give 7.5 g ofN-methoxycarbonylmethyl-N-trichloromethylthiobenzenesulfonamide, whichcrystallized as a colorless solid melting at 61°-62° C. The compound istabulated in Table I as Compound No. 1.

EXAMPLE 2 Preparation ofN-methoxycarbonylmethyl-N-(1,1,2,2-tetrachloroethylthio)cyclohexanesulfonamide

A 1.2 g (0.03 mol) sample of sodium hydroxide in 1.2 ml water was addeddropwise to a solution of 6.5 g (0.03 mol)N-(methoxycarbonylmethyl)cyclohexanesulfonamide, 7.0 g (0.03 mol)1,1,2,2-tetrachloroethylsulfenyl chloride, 0.5 g. triethylbenzylammoniumchloride in 100 ml dichloromethane. The resulting reaction mixture wasstirred at about 25° C. for 3 hours, washed with water, dried overmagnesium sulfate and evaporated under reduced pressure to give an oilresidue. The residue was chromatographed through silica gel. Elutionwith 10% ethyl ether/hexane gave 2.5 g of the product as an oil.Elemental analysis for C₁₁ H₁₇ Cl₄ NO₄ S₂ showed: %Cl, calc. 32.7, found32; %S, calc. 14.8, found 15.1. The product is tabulated in Table I asCompound No. 2.

EXAMPLE 3 Preparation ofN-[1-(ethoxycarbonyl)ethyl]-N-(1,1,2,2-tetrachloroethylthio)cyclohexanesulfonamide

A 9.2 g (0.05 mol) sample of cyclohexanesulfonyl chloride was addeddropwise to a solution of 7.7 g (0.05 mol) of the hydrochloride salt ofethyl 2-aminopropionate and 4 g (0.05 mol) sodium hydroxide in 14 mlwater and 100 ml acetonitrile. The reaction mixture was heated underreflux for 24 hours, cooled, filtered and evaporated under reducedpressure to give the crude product mixture. The product mixture wasdiluted with dichloromethane, washed with water, dried over magnesiumsulfate and dried under reduced pressure to give the crudeN-[1-(ethoxycarbonyl)ethyl]cyclohexanesulfonamide product.

A 1-g (0.02 mol, 50% in mineral oil) of sodium hydride was added insmall portions to 5 g of the crude sulfonamide product prepared above.The resulting reaction mixture was then added slowly to a stirredsolution of 4.7 g (0.02 mol) 1,1,2,2-tetrachloroethylsulfonyl chloridein 100 ml dichloromethane. The reaction mixture was stirred for anadditional hour and evaporated under reduced pressure to give a darkresidue. The residue was diluted with dichloromethane, washed withwater, dried over magnesium sulfate and evaporated under reducedpressure to give the crude product mixture. The product mixture waschromatographed through silica gel with 10% ethyl ether/90% hexaneelution to give 2.2 g ofN-[1-(ethoxycarbonyl)ethyl]-N-(1,1,2,2-tetrachloroethylthio)cyclohexanesulfonamide,as an oil. Elemental analysis for C₁₃ H₂₁ Cl₄ NO₄ S₂ showed: %Cl, calc.30.8, found 33.0; %S, calc. 12.9, found 13.4. The product is tabulatedin Table I as Compound No. 3.

EXAMPLE 4 Preparation ofN-phenyl-N-(1,1,2,2-tetrachloroethylthio)-methoxycarbonylmethylsulfonamide

A slurry of 217 g (2 mols) methyl chloroacetate and 252 g (2 mols)sodium sulfite in 500 ml water was stirred and heated under reflux forabout 2 hours. The resulting solution was allowed to stand at about 25°C. for 56 hours and then evaporated under reduced pressure to give solidresidue. The residue was washed with acetone and dried under vacuum at80°-90° C. to give crude sodium methoxycarbonylmethylsulfonate salt.

The sodium methoxycarbonylmethylsulfonate salt was added in smallportions to a stirred solution of 840 ml (9.14 mols) phosphorusoxychloride. The resulting mixture was then heated at 80°-100° C. forabout 5 hours and allowed to cool overnight. The reaction mixture wasfiltered, the filtered solid was washed with dichloromethane and thefiltrate distilled under reduced pressure to remove the dichloromethaneand excess phosphorus oxychloride. The resulting oil residue wasdistilled through a short Vigreaux column to give 226.8 g (65.7% yield)of methoxycarbonylmethylsulfonyl chloride, as a yellow oil, b.p. 79°-80°C. (0.5 mm Hg).

A 10-g (0.058 mol) sample of methoxycarbonylmethylsulfonyl chloride wasadded dropwise to a cooled (-8° C.) solution of 10.4 g (0.116 mol)aniline in 200 ml dichloromethane. The reaction mixture was allowed towarm to 25° C. and was stirred for 1 hour. The resultingN-phenyl-(methoxycarbonylmethyl)-sulfonamide product was filtered andwashed with ether. After drying, the product melted at 76°-77° C.

A 6.1 g (0.06 mol) sample of triethylamine was added dropwise to acooled (ice bath) solution of 13.8 g (0.06 mol)N-phenyl-(methoxycarbonylmethyl)sulfonamide and 14.1 g (0.06 mol)1,1,2,2-tetrachloroethylsulfenyl chloride in 200 ml dichloromethane. Thereaction mixture was then allowed to warm to 25° C., stirred for 3 hoursat 25° C., washed with water, dried over magnesium sulfate, andevaporated under reduced pressure to give the product mixture. Theproduct mixture was chromatographed through 300 g silica gel. Elutionwith 60% chloroform/40% hexane gave theN-phenyl-N-(1,1,2,2-tetrachloroethylthio)-methoxycarbonylmethyl)sulfonamideproduct, as a coloreless solid, m.p. 95°-96° C. This product istabulated in Table I as Compound No. 4.

EXAMPLE 5N,N-(dimethylcarbamylmethyl)-N-(1,1,2,2-tetrachloroethylthio)benzenesulfonamide

To a stirred solution of 23.0 gm (0.0949 mol)N,N-dimethylcarbamylmethylbenzenesulfonamide and 2.5 gm (0.01 mol)benzyl triethyl ammonium chloride in dichloromethane (300 ml) at icebath temperature was added 24.5 gm (0.104 mol) 1,1,2,2-tetrachloroethylsulfenyl chloride. To the resulting solution was added dropwise 8.3 gmconcentrated aqueous sodium hydroxide solution. The reaction mixture wasstirred at 5°-6° C. for one hour, washed with water, and dried overmagnesium sulfate. The solvent was removed in vacuo to give the productas a colorless solid (44.1 gm), m.p. 128°-129° C. Elemental analysis forC₁₂ H₁₄ Cl₄ N₂ O₃ S₂ showed: %Cl, calc. 32.22, found 30.5; %S, 14.57;found, 14.3. The product is tabulated in Table I as Compound No. 6.

The compounds tabulated in Table I were prepared by procedures similarto that of Examples 1-5. The structure of each compound tabulated inTable I was confirmed by elemental analysis and nuclear magneticresonance spectroscopy and/or infrared spectral analysis.

EXAMPLE 6 Mite Control Tests

Compounds of the invention were tested for the control mites and miteeggs by the following procedure.

Pinto bean leaves were invested with two spotted-mites (Tetramuchusurticae). The mites were then allowed to lay eggs on the leaves. After48 hours, the leaves were dipped into a water/acetone solutioncontaining a small amount of a nonionic surfactant and 40 ppm of thetest compound. The treated leaves were then maintained at 85° F. One dayafter treatment, the mortality of adult mites was determined, and sevendays after treatment, the egg mortality (non-hatching eggs) wasdetermined.

The results for the compounds found to have mite and mite egg controlactivity are tabulated in Table I.

EXAMPLE 7 Tomato Late Blight

Compounds of the invention were tested for the control of the TomatoLate Blight organism Phytophthora infestans conidia. Five- tosix-week-old tomato (variety Bonnt Best) seedlings were used. The tomatoplants were sprayed with a 250-ppm solution of the test compound inacetone, water and a small amount of a non-ionic emulsifier. The sprayedplants were then inoculated one day later with the organism, placed inan environmental chamber and incubated at 66°-68° F. and 100% relativehumidity for at least 16 hours. Following the incubation, the plantswere allowed to dry and then were maintained at 60-80% relative humidityfor approximately 7 days. The percent disease control provided by agiven test compound was based on the percent disease reduction relativeto untreated check plants. The compounds giving effective control at thetest concentration are tabulated in Table I.

EXAMPLE 8 Tomato Early Blight

Compounds of the invention were tested for the control of the TomatoEarly Blight organism, Alternaria solani conidia. Tomato (variety BonnyBest) seedlings of 6 to 7 weeks old were used. The tomato plans weresprayed with a 250-ppm solution of the test compound in anacetone-and-water solution containing a small amount of a non-ionicemulsifier. The sprayed plants were inoculated one day later with theorganism, dried and maintained at 60-80% relative humidity for about 12days. Percent disease control was based on the percent diseasedevelopment on untreated check plants. The compounds giving effectivecontrol at the test concentration are tabulated in Table I.

EXAMPLE 9 Celery Late Blight

Compounds of the invention were tested for the control of Celery LateBlight using celery (Utah) plants 11 weeks old. The Celery Late Blightorganism was Septoria apii. The celery plants were sprayed withsolutions of the candidate toxicant mixed with acetone, water and anonionic emulsifier. The plants were then inoculated with the organismand placed in an environmental chamber and incubated at 66°-68° F. in100% relative humidity for an extended period of time (approximately 48hours). Following the incubation, the plants are allowed to dry and thenwere maintained at a 60-80% relative humidity for approximately 14 days.The percent disease control provided by a given candidate toxicant isbased on the percent disease reduction relative to untreated checkplants. The compounds giving effective control at the testconcentrations are reported in Table I.

EXAMPLE 10 Powdery Mildew

The powdery mildew test was made using bean seedlings (var. Bountiful)with well-developed primary leaves. The pathogen was Erysiphe polygoni.The bean seedlings were sprayed with a 250-ppm solution of the testcompound in an acetone-water mixture containing a nonionic emulsifier.The treated plants were inoculatd one day after spray application of thetest compound with the pathogen. The plants were then maintained in agreenhouse at a 60-80% relative humidity and at a temperature of 68°-70°F. The rate of infection on the leaves was made after about 10 days. Thepercent disease control provided by a given test compound was based onthe disease reduction relative to untreated check plants. The compoundsof the invention giving effective control at the test concentrations arereported in Table I.

EXAMPLE 11 Botrytis cinerea control

Compound Nos. 1, 4, 5 and 7 of table I were tested for Botrytis cinereacontrol using detached, well-developed primary leaves of a 4-6 week oldhorsebean plant. The leaves were dipped into a 40-ppm solution of thetest compound in acetone and water containing a small amount of anonionic emulsifier, then taken out and placed in a petri plate linedwith two pieces of filter paper. The leaves were allowed to dry whilethe filter paper was kept moist by adding water as required. The treatedleaves were then inoculated with the spores of Botrytis cinerea fungusgrown on potato. The plate was covered after inoculation and kept at23.5° C. The filter-paper lining of the plate was kept saturated withwater throughout the test. The rate of disease incidence was determinedin 3 to 5 days, when the disease symptoms were fully evident onnon-treated check leaves. The percentage disease control provided by thetest compound was calculated as the percentage disease reduction basedon the non-treated check leaves. The results are tabulated in Table I.

EXAMPLE 11 Botrytis cinerea Mycelia Inhibition Test

Compound Nos. 2, 3, 6 and 8-14 of Table I were evaluated for fungicidaleffectiveness against Botrytis cinerea by means of a mycelial inhibitiontest. This test is designed to measure the fungitoxic activity in termsof their degree of inhibition of mycelium growth. Each compound to betested was dissolved in acetone to 500 ppm concentration. Paper stripswere innoculated with the particular mycelium growth by covering thepaper with a potato dextrose broth culture of mycelial suspension. Theinnoculated papers were then placed on potato dextrose agar plates andsprayed by means of a micro sprayer with the fungicidal solution. Thetreated paper strips were incubated at 25° C. and data is taken after 24hours. Fungicidal activities are measured by a zone of inhibitedmycelial growth from the center of the paper strip. The effectiveness ofthe compounds tested for fungicidal activity is reported in Table I interms of the percent control of the fungus.

                                      TABLE I                                     __________________________________________________________________________     ##STR3##                                                                                                                 Mite                                                  Melting                 Control, %                        No.                                                                              R       R.sup.1  Point, °C.                                                                   TLB.sup.a                                                                         PM.sup.b                                                                         CLB.sup.c                                                                         TEB.sup.d                                                                         BC.sup.e                                                                         Adult                                                                             Eggs                          __________________________________________________________________________    1* φ                                                                                  ##STR4##                                                                              61-62 --  88 0   37  16*                                                                              0   0                                 ##STR5##                                                                              ##STR6##                                                                              oil   98  97 --  0   100                                  3                                                                                 ##STR7##                                                                              ##STR8##                                                                              oil   50  100                                                                              --  0   100                                                                              0   100                           4                                                                                 ##STR9##                                                                             φ    97-98 98  0  --  0   44*                                                                              0   96                            5  φ                                                                                  ##STR10##                                                                             105-107                                                                             82  99 97  --  57*                                                                              98  100                           6  φ                                                                                  ##STR11##                                                                             130-131                                                                             67  0  95  65  96 22  39                            7*                                                                                ##STR12##                                                                            φ    118-119                                                                             83  0  --  91  0* 0   0                             8  4-CH.sub.3 φ                                                                       ##STR13##                                                                             106-107                                                                             99  90 99  71  100                                                                              0   100                           9  φ                                                                                  ##STR14##                                                                             oil   97  85 95  96  59 0   100                           10                                                                                ##STR15##                                                                            4-CH.sub.3 φ                                                                       115-116                                                                             --  0  --  75  68 0   50                            11                                                                                ##STR16##                                                                            3,5-(CF.sub.3).sub.2 φ                                                             92-93 --  0  --  44  48 0   39                            12                                                                                ##STR17##                                                                            φ    114-116                                                                             99  29 97  --  90 0   100                           13*                                                                               ##STR18##                                                                            φ    120-124                                                                             76  14 44  --  55 0   0                             14                                                                                ##STR19##                                                                            3-CH.sub.3 φ                                                                       91-92 85  0  91  63  100                                                                              15  70                            __________________________________________________________________________     φ = phenyl                                                                *M-218                                                                        .sup.a = Tomato Late Blight                                                   .sup.b = Powdery Mildew                                                       .sup.c = Celery Late Blight                                                   .sup.d = Tomato Early Blight                                                  .sup.e = Botrytis Cinerea                                                     *This compound is substituted with SCCl.sub.3 instead of SCCl.sub.3           Cl.sub.2 H.                                                              

What is claimed is:
 1. A compound of the formula ##STR20## wherein R isphenyl substituted with up to 2 of the same or different substituentsselected from fluoro, chloro, bromo, iodo, trifluoromethyl,trichloromethyl, tribromomethyl or alkyl of 1 to 4 carbon atoms; R¹ iscarbamylalkyl of 1 to 6 carbon atoms; N-alkylcarbamylalkyl of 2 to 6carbon atoms; or N,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms; and R²is alkyl of 1 to 2 carbon atoms and of 1 to 5 fluoro, chloro, bromo oriodo atoms.
 2. A method for killing mite eggs which comprises applyingthereto an ovicidally effective amount of a compound of the formula##STR21## wherein R is alkyl of 1 to 6 carbon atoms; cycloalkyl of 5 to8 carbon atoms substituted with up to 2 alkyl of 1 to 4 carbon atoms;phenyl substituted with up to 2 of the same or different substituentsselected from fluoro, chloro, bromo, iodo, trifluoromethyl,trichloromethyl, tribromomethyl or alkyl of 1 to 4 carbon atoms;alkoxycarbonylalkyl of 2 to 6 carbon atoms; carbamylalkyl of 1 to 6carbon atoms; N-alkylcarbamylalkyl of 2 to 6 carbon atoms; orN,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms; R¹ is alkyl of 1 to 6carbon atoms; cycloalkyl of 5 to 8 carbon atoms substituted with up to 2alkyl of 1 to 4 carbon atoms; phenyl substituted with up to 2 of thesame or different substituents selected from fluoro, chloro, bromo,iodo, trifluoromethyl, trichloromethyl, tribromomethyl or alkyl of 1 to4 carbon atoms; alkoxycarbonyl of 2 to 6 carbon atoms; carbamylalkyl of1 to 6 carbon atoms, N-alkylcarbamylalkyl of 2 to 6 carbon atoms;N,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms; and R² istetrachloroethyl, with the proviso that one R or R¹ group isalkoxycarbonylalkyl, carbamylalkyl, N-alkylcarbamylalkyl orN,N-dialkylcarbamylalkyl.
 3. A method for the control of fungi whichcomprises applying thereto a fungicidally effective amount of a compoundof the formula ##STR22## wherein R is alkyl of 1 to 6 carbon atoms;cycloalkyl of 5 to 8 carbon atoms substituted with up to 2 alkyl of 1 to4 carbon atoms; phenyl substituted with up to 2 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, trifluoromethyl,trichloromethyl, tribromomethyl or alkyl of 1 to 4 carbon atoms;alkoxycarbonylalkyl of 2 to 6 carbon atoms; carbamylalkyl of 1 to 6carbon atoms; N-alkylcarbamylalkyl of 2 to 6 carbon atoms; orN,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms; R¹ is alkyl of 1 to 6carbon atoms; cycloalkyl of 5 to 8 carbon atoms substituted with up to 2alkyl of 1 to 4 carbon atoms; phenyl substituted with up to 2 of thesame or different substituents selected from fluoro, chloro, bromo,iodo, trifluoromethyl, trichloromethyl, tribromomethyl, or alkyl of 1 to4 carbon atoms; alkoxycarbonylalkyl of 2 to 6 carbon atoms;carbamylalkyl of 1 to 6 carbon atoms; N-alkylcarbamylalkyl of 2 to 6carbon atoms; or N,N-dialkylcarbamylalkyl of 3 to 6 carbon atoms; and R²is alkyl of 1 to 2 carbon atoms and of 1 to 5 fluoro, chloro, bromo oriodo atoms, with the proviso that one R or R¹ group isalkoxycarbonylalkyl, carbamylalkyl of 1 to 6 carbon atoms,N-alkylcarbamylalkyl of 2 to 6 carbon atoms or N,N-dialkylcarbamylalkylof 3 to 6 carbon atoms.
 4. The compound according to claim 1 wherein Ris phenyl, R¹ is N,N-dimethylcarbamylmethyl and R² is1,1,2,2-tetrachloroethyl.